CN113000034A - 基于天然植物多酚复合涂层的铀离子亲和膜的制备方法 - Google Patents

基于天然植物多酚复合涂层的铀离子亲和膜的制备方法 Download PDF

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CN113000034A
CN113000034A CN202110204169.9A CN202110204169A CN113000034A CN 113000034 A CN113000034 A CN 113000034A CN 202110204169 A CN202110204169 A CN 202110204169A CN 113000034 A CN113000034 A CN 113000034A
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吴铭榜
马璐琳
叶昊
姚菊明
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Abstract

本发明公开了一种基于天然植物多酚复合涂层的铀离子亲和膜的制备方法。将超疏水的聚合物多孔基膜在乙醇中浸润后取出,用滤纸吸去膜表面多余的乙醇溶液;将用乙醇处理过的聚合物多孔基膜置于一定浓度的植酸溶液中,使膜表面充分吸附植酸溶液,静置后取出;再将取出后的聚合物多孔基膜置于一定浓度和PH的蛋白质溶液中,使蛋白质变性固化,在膜表面形成固化的杂化涂层,静置后取出;不断重复沉积步骤,然后用超纯水漂洗后,真空烘干即得到铀离子亲和膜。本发明的铀亲和膜,具有高亲水性、高铀吸附性能和良好的通量和回复能力。

Description

基于天然植物多酚复合涂层的铀离子亲和膜的制备方法
技术领域
本发明涉及基材改性技术领域的一种改性膜制备方法,尤其涉及一种用于海水提铀的铀亲和膜。
背景技术
目前海水提铀的方法有很多种,主要包括有吸附法、电化学法、生物处理法、离子交换法、超导磁分离法等。而吸附法是目前研究最多的方法之一,吸附法海水提铀的研究重点是研究开发新型铀吸附材料。由于制备简单、成本低、效率高,被广泛应用于海水提铀领域。而吸附法的核心是选择和制备性能优良的吸附材料。目前实际商业中应用最广泛的就是通过纤维状吸附剂。目前,基材改性的方法主要是氢键诱导接枝、高能辐射接枝以及化学诱导接枝、沉积法等。
例如,公开号为CN105688828B的中国专利公开了一种采用磷酸改性铁树叶制备海水提铀植物-无机复合吸附剂的方法。所述海水提铀生物吸附剂由铁树叶片干燥粉碎后,经磷酸改性,再将所得产物洗涤、干燥、活化后得到。在pH值为8.7、温度为25℃、吸附平衡时间为240min的条件下,应用其对模拟海水中铀进行吸附,能获得较高的吸附效率。吸附铀后,再采用0.08mol/L硝酸进行解吸后,该吸附剂又可重新利用,并能保持较高的吸附效率。该吸附剂具有材料来源广、制备简单、成本低、吸附效果好、解吸容易、机械强度大、环境污染小等多重优点。
公开号为CN107138137B的中国专利公开了一种抗菌性海水提铀吸附剂,通过接枝共聚方法将季铵盐单体和丙烯腈单体接枝到天然纤维单体上,然后进行羟胺化制备而成,所得吸附剂季铵基团含量为0.1~1.0mmol/g,偕胺肟基团含量为0.2~7.5mmol/g。本发明还公开了上述抗菌性海水提铀吸附剂的制备方法,制备时,原料组分有:天然纤维材料10份、丙烯腈10~90份、乙烯基类季铵盐10~90份、氧化还原引发体系氧化剂1~5份,还原剂1~5份,盐酸羟胺10~30份,去离子水300~600份,各组分的配比按质量份计;工艺步骤包括氧化还原引发体系下接枝反应,接枝产物偕胺肟化反应。本发明所述的抗菌性海水提铀吸附剂纤维基材来源丰富,天然可再生,价格低廉,制备成本低,吸附材料对大肠杆菌和金黄色葡萄球菌的抑菌率均达到95%以上。相对于常规海水提铀吸附剂,所得材料对铀酰离子的吸附量增加约25%。
公开号为CN102614842A的中国专利公开了一种海水提铀用螯合纤维吸附剂的制备方法,该方法包括下述步骤:(1)将超高分子量聚乙烯纤维进行辐照处理,所述辐照源为钴源或电子束;(2)将辐照后的超高分子量聚乙烯纤维与含有接枝单体的溶液混合通过接枝聚合反应获得接枝聚丙烯腈改性纤维,所述接枝单体为纯丙烯腈,或丙烯酸与丙烯腈的混合单体,所述混合单体中丙烯酸与丙烯腈的摩尔含量比小于等于1∶2;(3)将接枝聚丙烯腈纤维进行胺肟化反应,使氰基转化为偕胺肟基,制得螯合纤维吸附剂。本发明还提供了一种通过上述制备方法获得的螯合纤维吸附剂,该吸附剂既较好的继承了超高分子量聚乙烯纤维的优良力学性能,又具有较高的吸附铀的性能,并且可以长期反复用于海水提铀。
公开号为CN105771921B的中国专利公开了本发明涉及一种采用磷酸三丁酯改性樟树叶制备海水提铀植物-有机复合吸附剂的方法。通过磷酸三丁酯对植物叶片粉末进行改性,再将所得产物活化洗涤真空干燥后得到植物有机复合吸附剂,该吸附剂应用于吸附海水铀方面。吸附剂原材料来源广泛、取材方便、制备过程简单、仪器设备要求不高、成本较低;用于海水铀吸附,吸附效率高,吸附容量大;吸附速率很快,短时间内即达到吸附平衡;在成分复杂的碱性海水溶液环境中对铀具有较高的选择特异吸附性能。
已经报道的用于海水提铀的吸附剂中,PP、PE等廉价且具有超高机械强度的连续纤维状吸附剂被广泛应用于海水提铀吸附剂中,而对于这类纤维多孔膜的改性方法主要包括氢键诱导接枝、高能辐射接枝以及化学诱导接枝。目前使用最多的是利用辐射接枝的方法改性基材用于海水提铀。而利用沉积法改性基材并用于海水提铀的方法则较少。
发明内容
为了解决背景技术中存在的问题,本发明提供了一种基于天然植物多酚复合涂层的铀离子亲和膜的制备方法,获得了吸附效果优异的铀离子亲和膜,该制备方法可控性强。
本发明所采用的技术方案是:
(1)将超疏水的聚合物多孔基膜在乙醇中浸润一段时间后取出,用滤纸吸去膜表面多余的乙醇溶液;
(2)将用乙醇处理过的聚合物多孔基膜置于一定浓度的植酸溶液中,使膜表面充分吸附植酸溶液,静置一段时间后取出;
(3)再将取出后的聚合物多孔基膜置于一定浓度和PH的蛋白质溶液中,使蛋白质变性固化,在膜表面形成固化的杂化涂层,静置一段时间后取出,此为一次沉积;
(4)不断重复步骤(3)1-3次,然后用超纯水漂洗后,真空烘干即得到铀离子亲和膜。
所述(1)中,聚合物多孔基膜为PP膜、PE膜、PVDF膜、PVC膜中的至少一种。
所述(2)中,植酸溶液的浓度为2.0~10.0mg/g。
所述(3)中,蛋白质溶液为溶菌酶、OVA、BSA、g-球蛋白、胰岛素中的至少一种。
所述(3)中,蛋白质溶液的浓度为2.0~10.0mg/g,PH为4~10。
所述的植酸和蛋白质的比例为1:1~1:6。
在乙醇中浸润时间为1~60min,在植酸溶液浸泡时间为1~12h,蛋白质溶液中的浸泡时间为1~12h。
本发明用该制备方法制得的铀离子亲和膜的应用领域包括海水提铀等。
将超疏水的聚合物多孔基膜在乙醇中浸润后取出,用滤纸吸去膜表面多余的乙醇溶液;将用乙醇处理过的聚合物多孔基膜置于一定浓度的植酸溶液中,使膜表面充分吸附植酸溶液,静置后取出;再将取出后的聚合物多孔基膜置于一定浓度和PH的蛋白质溶液中,使蛋白质变性固化,在膜表面形成固化的杂化涂层,静置后取出;不断重复沉积步骤,然后用超纯水漂洗后,真空烘干即得到铀离子亲和膜。
本发明具有以下优点及应用前景:
与现有技术相比,本发明的有益效果为:
(1)相比于工业界主要采用的高能辐射接枝改性法,该制备方法更加简单,并且不会破坏基材,取得了更优异的吸附效果;
(2)该制备方法简单,绿色温和且保形;
(3)本发明的制备方法中,基材可选用常用的超疏水基膜,优选的,选用PP膜,其价格低廉,并且具有超高的机械强度,可广泛应用于工业化生产。
该铀亲和膜可应用于海水提铀。
附图说明
图1为本发明的制备方法的原理示意图。
具体实施方式
通过以下实施例对本发明做更详细的描述,但所述实施例不构成对本发明的限制。
其反应的机理如图1所示,将疏水性的聚合物多孔基膜在乙醇中浸润一段时间后取出,用滤纸吸干膜表明多余的乙醇溶液。然后将基膜置于一定浓度的植酸溶液中,使膜表面充分吸附植酸溶液,静置一段时间后取出。再将基膜置于一定浓度和PH的蛋白质溶液中,使蛋白质变性固化,在膜表面形成固化的杂化涂层,静置一段时间后取出,此为一次沉积。然后用超纯水漂洗后,真空烘干即得到铀离子亲和膜。
本发明所制备的铀亲和膜用于海水提铀,接触角、铀吸附量、水通量及其恢复率是评价膜性能的四个重要参数。
液体在固体材料表面上的接触角,是衡量该液体对材料表面润湿性能的重要参数。若θ<90°,则固体表面是亲水性的,即液体较易润湿固体,其角越小,表示润湿性越好;若θ>90°,则固体表面是疏水性的,即液体不容易润湿固体,容易在表面上移动。
在初始U(VI)浓度为10ppm的2L溶液中进行吸附等温线研究。将溶液pH调至6,在压力为0.4MPa,水流量为20L/h的循环水下吸附12h进行吸附实验。达到吸附平衡后分析U(VI)的浓度,计算得到吸附容量,公式为:
Figure BDA0002949180340000041
其中C0和Ce分别表示初始和平衡U(VI)浓度,单位为mg·L-1;V表示U(VI)溶液的体积,单位为L;m表示吸附剂的用量,单位为g。
水通量的定义为:在一定操作压力条件下,单位时间内透过单位膜面积的水的体积,其单位为Lm-2h-1,公式为:
Figure BDA0002949180340000042
其中,V表示透过的溶液的体积,单位为L;A表示有效膜面积,单位为m2;t表示时间,单位为h。
实施例1
将聚丙烯(PP)膜浸渍在乙醇中0.5小时,随后用滤纸吸干膜表面多余的乙醇溶液;将上述乙醇处理过PP膜置于浓度为10mg/mL的植酸溶液12小时;浸渍结束后,将PP膜置于浓度为10mg/mL,pH=7的溶菌酶溶液3小时,植酸溶液与溶菌酶溶液浓度比为1:1;反应结束后,用超纯水洗涤数次,真空烘干即得铀酰离子亲和膜;将铀酰离子亲和膜进行接触角、吸附性能、水通量及其恢复能力进行测试,结果表明:膜接触角为13°、铀酰离子吸附量1235.97mg/g、水通量5712.31Lm-2h-1、恢复率95%。
实施例2~4
分别将聚乙烯(PE)膜、聚偏氟乙烯(PVDF)膜、聚氯乙烯(PVC)膜作为基膜,其余条件同实施例1。
Figure BDA0002949180340000051
实施例5~12
选用的植酸浓度为2.0、3.0、4.0、5.0、7.0、8.0、9.0mg/g,其余条件同实施例1。
Figure BDA0002949180340000052
实施例13~20
选用的溶菌酶溶液浓度为2.0、3.0、4.0、5.0、6.0、7.0、8.0、9.0mg/mL,其余条件同实施例1。
Figure BDA0002949180340000053
Figure BDA0002949180340000061
实施例21~24
分别选用卵清蛋白(OVA)、牛血清蛋白(BSA)、g-球蛋白、胰岛素蛋白做为蛋白质,其余条件同实施例1。
Figure BDA0002949180340000062
实施例25~29
分别选用植酸与蛋白质的浓度比例为1:2、1:3、1:4、1:5、1:6,其余条件同实施例1。
Figure BDA0002949180340000063
实施例30~35
分别选用pH为4、5、6、8、9、10的溶菌酶溶液,其余条件同实施例1。
Figure BDA0002949180340000064
Figure BDA0002949180340000071
实施例36~39
基膜在植酸中浸泡时间分别为1、3、6、9小时,其余条件同实施例1。
Figure BDA0002949180340000072
实施例40~43
基膜在蛋白质溶液中浸泡时间分别为1、6、9、12小时,其余条件同实施例1。
Figure BDA0002949180340000073
实施例44~46
将实施例1实验步骤的循环次数分别设置为2、3、4次,其余条件同实施例1。
Figure BDA0002949180340000074
由此实施可见,本发明的铀亲和膜,具有高亲水性、高铀吸附性能和良好的通量和回复能力,可应用于海水提铀、放射性废水处理、环境修复等方面。制备方法操作简单,便于工业化生产。

Claims (7)

1.一种基于天然植物多酚复合涂层的铀离子亲和膜的制备方法,其特征在于:包括以下步骤:
(1)将超疏水的聚合物多孔基膜在乙醇中浸润一段时间后取出,用滤纸吸去膜表面多余的乙醇溶液;
(2)将用乙醇处理过的聚合物多孔基膜置于一定浓度的植酸溶液中,使膜表面充分吸附植酸溶液,静置一段时间后取出;
(3)再将取出后的聚合物多孔基膜置于一定浓度和PH的蛋白质溶液中,使蛋白质变性固化,在膜表面形成固化的杂化涂层,静置一段时间后取出;
(4)不断重复步骤(3)1-3次,然后用超纯水漂洗后,真空烘干即得到铀离子亲和膜。
2.根据权利要求1所述的一种基于天然植物多酚复合涂层的铀离子亲和膜的制备方法,其特征在于:所述(1)中,聚合物多孔基膜为PP膜、PE膜、PVDF膜、PVC膜中的至少一种。
3.根据权利要求1所述的一种基于天然植物多酚复合涂层的铀离子亲和膜的制备方法,其特征在于:所述(2)中,植酸溶液的浓度为2.0~10.0mg/g。
4.根据权利要求1所述的一种基于天然植物多酚复合涂层的铀离子亲和膜的制备方法,其特征在于:所述(3)中,蛋白质溶液为溶菌酶、OVA、BSA、g-球蛋白、胰岛素中的至少一种。
5.根据权利要求1所述的一种基于天然植物多酚复合涂层的铀离子亲和膜的制备方法,其特征在于:所述(3)中,蛋白质溶液的浓度为2.0~10.0mg/g,PH为4~10。
6.根据权利要求1所述的一种基于天然植物多酚复合涂层的铀离子亲和膜的制备方法,其特征在于:所述的植酸和蛋白质的比例为1:1~1:6。
7.根据权利要求1所述的一种基于天然植物多酚复合涂层的铀离子亲和膜的制备方法,其特征在于:在乙醇中浸润时间为1~60min,在植酸溶液浸泡时间为1~12h,蛋白质溶液中的浸泡时间为1~12h。
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